Low-tack ophthalmic and otorhinolaryngological device materials

ABSTRACT

Disclosed are soft, high refractive index, acrylic materials. These materials, especially useful as intraocular lens materials, contain an aryl acrylic hydrophobic monomer as the single principal device-forming monomer and a tack-reducing macromer additive. In addition to their use as intraocular lens materials, the present materials are also suitable for use in other ophthalmic or otorhinolaryngological devices, such as contact lenses, keratoprostheses, corneal inlays or rings; otological ventilation tubes and nasal implants.

This application claims priority to U.S. Provisional Application, U.S.Ser. No. 60/832,478 filed Jul. 21, 2006.

FIELD OF INVENTION

This invention is directed to acrylic device materials. In particular,this invention relates to low-tack, high refractive index acrylic devicematerials particularly suited for use as intraocular lens (“IOL”)materials.

BACKGROUND OF INVENTION

With the recent advances in small-incision cataract surgery, increasedemphasis has been placed on developing soft, foldable materials suitablefor use in artificial lenses. In general, these materials fall into oneof three categories: hydrogels, silicones, and acrylics.

In general, hydrogel materials have a relatively low refractive index,making them less desirable than other materials because of the thickerlens optic necessary to achieve a given refractive power. Siliconematerials generally have a higher refractive index than hydrogels, buttend to unfold explosively after being placed in the eye in a foldedposition. Explosive unfolding can potentially damage the cornealendothelium and/or rupture the natural lens capsule. Acrylic materialsare desirable because they typically have a higher refractive index thansilicone materials and unfold more slowly or controllably than siliconematerials.

U.S. Pat. No. 5,290,892 discloses high refractive index, acrylicmaterials suitable for use as an IOL material. These acrylic materialscontain, as principal components, two aryl acrylic monomers. They alsocontain a cross-linking component. The IOLs made of these acrylicmaterials can be rolled or folded for insertion through small incisions.

U.S. Pat. No. 5,331,073 also discloses soft acrylic IOL materials. Thesematerials contain as principal components, two acrylic monomers whichare defined by the properties of their respective homopolymers. Thefirst monomer is defined as one in which its homopolymer has arefractive index of at least about 1.50. The second monomer is definedas one in which its homopolymer has a glass transition temperature lessthan about 22° C. These IOL materials also contain a cross-linkingcomponent. Additionally, these materials may optionally contain a fourthconstituent, different from the first three constituents, which isderived from a hydrophilic monomer. These materials preferably have atotal of less than about 15% by weight of a hydrophilic component.

U.S. Pat. No. 5,693,095 discloses foldable ophthalmic lens materialscomprising a total of at least 90% by weight of only two principallens-forming monomers. One lens-forming monomer is an aryl acrylichydrophobic monomer. The other lens-forming monomer is a hydrophilicmonomer. The lens materials also comprise a cross-linking monomer andoptionally comprise a UV absorber, polymerization initiators, reactiveUV absorbers and reactive blue-light absorbers.

U.S. Pat. No. 6,653,422 discloses foldable ophthalmic lens materialsconsisting essentially of a single device-forming monomer and at leastone cross-linking monomer. The materials optionally contain a reactiveUV absorber and optionally contain a reactive blue-light absorber. Thesingle device-forming monomer is present in an amount of at least about80% by weight. The device-forming monomer is an aryl acrylic hydrophobicmonomer.

Some foldable acrylic materials are tacky. Foldable ophthalmic lensesmade of tacky acrylic materials are difficult to handle. Attempts havebeen made to reduce tackiness so that the lenses are easier to processor handle, easier to fold or deform, and have shorter unfolding times.For example, U.S. Pat. No. 6,713,583 discloses ophthalmic lenses made ofa material that includes branched chain alkyl groups in an amounteffective to reduce tackiness. U.S. Pat. No. 4,834,750 disclosesintraocular lenses made from materials that optionally include afluoroacrylate component to reduce surface tackiness. U.S. Pat. No.5,331,073 discloses acrylic materials that optionally include ahydrophilic component that is present in an amount sufficient to reducethe materials' tackiness. U.S. Pat. No. 5,603,774 discloses a plasmatreatment process for reducing the tackiness of a soft acrylic article.

SUMMARY OF THE INVENTION

Improved soft, foldable acrylic materials which are particularly suitedfor use as IOLs, but which are also useful as other ophthalmic orotorhinoloaryngological devices, such as contact lenses,keratoprostheses, corneal rings or inlays, otological ventilation tubesand nasal implants have now been discovered. These materials containonly one principal lens-forming component, an aryl acrylic hydrophobicmonomer, in an amount of at least about 75% by weight. The materialsalso contain a macromer additive in an amount sufficient to reduce thematerials' tackiness. The macromer additive is adimethylacryloxypropyl-terminated polydimethylsiloxane macromer. Theremainder of the material comprises a cross-linking monomer andoptionally one or more additional components selected from the groupconsisting of UV-light absorbing compounds and blue-light absorbingcompounds.

DETAILED DESCRIPTION OF THE INVENTION

The ophthalmic or otorhinolaryngological device materials of the presentinvention comprise only one principal device-forming monomer. Forconvenience, the device-forming monomer may be referred to as alens-forming monomer, particularly with reference to an IOL. Thematerials of the present invention, however, are also suitable for useas other ophthalmic or otorhinolaryngological devices such as contactlenses, keratoprostheses, corneal inlays or rings, otologicalventilation tubes and nasal implants.

The aryl acrylic hydrophobic monomers suitable for use as the principallens-forming monomer in the materials of the present invention have theformula

wherein:

-   -   A is H, CH₃, CH₂CH₃, or CH₂OH;    -   B is (CH₂)_(m) or [O(CH₂)₂]_(n);    -   C is (CH₂)_(w);    -   m is 2-6;    -   n is 1-10;    -   Y is nothing, O, S, or NR, provided that if Y is O, S, or NR,        then B is (CH₂)_(m);    -   R is H, CH₃, C_(n)H_(2n+1) (n=1-10), iso-OC₃H₇, C₆H₅, or        CH₂C₆H₅;    -   w is 0-6, provided that m+w≦8; and    -   D is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₆H₅, CH₂C₆H₅ or halogen.

Preferred aryl acrylic hydrophobic monomers for use in the materials ofthe present invention are those wherein A is CH₃, B is (CH₂)_(m), m is2-5, Y is nothing or O, w is 0-1, and D is H. Most preferred are4-phenylbutyl methacrylate, 5-phenylpentyl methacrylate,2-benzyloxyethyl methacrylate, and 3-benzyloxypropyl methacrylate.

Monomers of structure I can be made by known methods. For example, theconjugate alcohol of the desired monomer can be combined in a reactionvessel with methyl methacrylate, tetrabutyl titanate (catalyst), and apolymerization inhibitor such as 4-benzyloxy phenol. The vessel can thenbe heated to facilitate the reaction and distill off the reactionby-products to drive the reaction to completion. Alternative synthesisschemes involve adding methacrylic acid to the conjugate alcohol andcatalyzing with a carbodiimide or mixing the conjugate alcohol withmethacryloyl chloride and a base such as pyridine or triethylamine.

The materials of the present invention comprise a total of at leastabout 75%, preferably at least about 80%, by weight or more of theprincipal lens-forming monomer.

In addition to the principal lens-forming monomer, the materials of thepresent invention contain a macromer additive in an amount sufficient toreduce the material's tackiness. Generally, the amount of macromeradditive in the materials of the present invention will range from0.5-3.9% (w/w), and preferably will range from 0.5-2% (w/w), mostpreferably 0.8-1.2% (w/w). The macromer is adimethylacryloxypropyl-terminated polydimethylsiloxane macromer of theformula:

wherein

-   R₁ and R₂ are independently —CH₃, —CH₂CH₃, —CH₂CH₂CH₂CH₃,    CH₂CH₂CH₂CH₃, —C₆H₅, —CH₂C₆H₅, —CH₂CH₂C₆H₅, —CH₂CH₂CH₂C₆H₅, or    —CH₂CH₂CH₂CH₂C₆H₅;-   R₃ is H, CH₃, or CH₂CH₃;-   z is 2-11; and-   x indicates the number of repeating units and determines the    molecular weight of the macromer.

Preferred macromers are those wherein

-   R₁═R₂═CH₃;-   R₃ is H, CH₃, or CH₂CH₃; and-   z=3; and-   x=0-43.

More preferred macromers are those wherein R₁, R₂, R₃, and z are asdefined above for the preferred macromers and x is 0-22. In oneembodiment, x is 5-14 (generally corresponding to a macromer molecularweight (M_(n)) of 800-1400). In another embodiment, x is 2-5 (generallycorresponding to a macromer molecular weight (M_(n)) of 550-700).

Dimethylacryloxypropyl-terminated polydimethylsiloxanes of the aboveformula (“PDMS”), also known as methacryloxypropyl terminatedpolydimethyl siloxanes, can be made by known methods. Some PDMScompounds are commercially available from Gelest, Inc. in molecularweights (M_(n)) ranging from 800-1400 (mid-range M_(n) estimated as1000). There are higher (M_(n) 4K-6K, 5K-20K, 20K -30K) and lower (M_(n)386, 550-700) molecular weight grades of dimethacryloxypropyl-terminatedsiloxane commercially available. The macromer additive selection islimited by solubility (in the remainder of the copolymer materialformulation) and formulation clarity (the copolymer material should beclear). Generally, PDMS used in the present invention will have amolecular weight (M_(n)) of about 300-about 3500 and preferably about350-about 2000. In one embodiment, an especially preferred PDMS has aM_(n) from about 800-about 1400. In another embodiment, an especiallypreferred PDMS has a M_(n) from about 550-about 700.

The copolymer materials of the present invention are cross-linked. Thecopolymerizable cross-linking agent used in the copolymers of thisinvention may be any terminally ethylenically unsaturated compoundhaving more than one unsaturated group. Suitable cross-linking agentsinclude, for example: ethylene glycol dimethacrylate; diethylene glycoldimethacrylate; allyl methacrylate; 1,3-propanediol dimethacrylate;2,3-propanediol dimethacrylate; 1,6-hexanediol dimethacrylate;1,4-butanediol dimethacrylate;CH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ where p=1-50; andCH₂═C(CH₃)C(═O)O(CH₂)_(t)O—C(═O)C(CH₃)═CH₂ where t=3-20; and theircorresponding acrylates. A preferred cross-linking monomer isCH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ where p is such that thenumber-average molecular weight is about 400, about 600, or about 1000.The most preferred cross-linking agent isCH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ where p is such that thenumber-average molecular weight is about 1000 (“PEG(1000)DMA”).

The chosen cross-linking agent should be soluble in the chosen monomerof structure I to minimize curing problems. When p approaches the upperend of the range of 1-50, theCH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ cross-linker may not besoluble at desired levels in some monomers of structure I, even with theaid of heat or sonication.

Generally, only one cross-linking monomer will be present in the devicematerials of the present invention. In some cases, however, combinationsof cross-linking monomers may be desirable. A preferred combination ofcross-linking monomers is PEG(1000)DMA and ethylene glycoldimethacrylate (“EGDMA”).

Generally, the total amount of the cross-linking component is at least0.1% by weight and, depending on the identity and concentration of theremaining components and the desired physical properties, can range toabout 20% by weight. The preferred concentration range for thecross-linking component is 0.1-17% (w/w).

In addition to the aryl acrylic hydrophobic lens-forming monomer, themacromer additive, and the cross-linking component, the lens material ofthe present invention may also contain a total of up to about 10% byweight of additional components which serve other purposes, such asreactive UV and/or blue-light absorbers.

Preferred reactive UV absorbers are2-(2′-hydroxy-3′-methallyl-5′-methylphenyl)benzotriazole, commerciallyavailable as o-Methallyl Tinuvin P (“oMTP”) from Polysciences, Inc.,Warrington, Pa., and2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenylethyl]methacrylate (“BHMA”).UV absorbers are typically present in an amount from about 0.1-5% (w/w).

Suitable reactive blue-light absorbing compounds are those described inU.S. Pat. No. 5,470,932, the entire contents of which are herebyincorporated by reference. Blue-light absorbers are typically present inan amount from about 0.01-0.5% (w/w).

Suitable polymerization initiators include thermal initiators andphotoinitiators. Preferred thermal initiators include peroxyfree-radical initiators, such as t-butyl (peroxy-2-ethyl)hexanoate anddi-(tert-butylcyclohexyl) peroxydicarbonate (commercially available asPerkadoxe® 16 from Akzo Chemicals Inc., Chicago, Ill.). Particularly incases where the lens material does not contain a blue-light absorbingchromophore, preferred photoinitiators include benzoylphosphine oxidephotoinitiators, such as the blue-light initiator2,4,6-trimethyl-benzoyidiphenylphosphine oxide, commercially availableas Lucirin® TPO from BASF Corporation (Charlotte, N.C.). Initiators aretypically present in an amount of about 5% (w/w) or less. Becausefree-radical initiators do not become chemically a part of the polymersformed, the total amount of initiator is customarily not included whendetermining the amounts of other ingredients.

The identity and amount of the principal lens-forming monomer describedabove and the identity and amount of any additional components aredetermined by the desired properties of the finished ophthalmic lens.Preferably, the ingredients and their proportion are selected so thatthe acrylic lens materials of the present invention possess thefollowing properties, which make the materials of the present inventionparticularly suitable for use in IOLs which are to be inserted throughincisions of 5 mm or less.

The lens material preferably has a refractive index in the dry state ofat least about 1.50 as measured by an Abbe' refractometer at 589 nm (Nalight source). For a given optic diameter, optics made from materialshaving a refractive index lower than 1.50 are necessarily thicker thanoptics of the same power which are made from materials having a higherrefractive index. As such, IOL optics made from materials having arefractive index lower than about 1.50 generally require relativelylarger incisions for IOL implantation.

The glass-transition temperature (“Tg”) of the lens material, whichaffects the material's folding and unfolding characteristics, ispreferably below about 25° C., and more preferably below about 15° C. Tgis measured by differential scanning calorimetry at 10° C./min., and isdetermined as the half-height of the heat capacity increase.

The lens material will have an elongation (strain at break) of at least75%, preferably at least 90%, and most preferably at least 100%. Thisproperty indicates that the lens generally will not crack, tear or splitwhen folded. Elongation of polymer samples is determined on dumbbellshaped tension test specimens with a 20 mm total length, length in thegrip area of 11 mm, overall width of 2.49 mm, 0.833 mm width of thenarrow section, a fillet radius of 8.83 mm, and a thickness of 0.9 mm.Testing is performed on samples at standard laboratory conditions of23±2° C. and 50±5% relative humidity using a tensile tester. The gripdistance is set at 11 mm and a crosshead speed is set at 500 mm/minuteand the sample is pulled to failure. The strain at break is reported asa fraction of the displacement at failure to the original grip distance.Stress at break is calculated at the maximum load for the sample,typically the load when the sample breaks, assuming that the initialarea remains constant. The Young's modulus is calculated from theinstantaneous slope of the stress-strain curve in the linear elasticregion. The 25% secant modulus is calculated as the slope of a straightline drawn on the stress-strain curve between 0% strain and 25% strain.The 100% secant modulus is calculated as the slope of a straight linedrawn on the stress-strain curve between 0% strain and 100% strain.

IOLs constructed of the materials of the present invention can be of anydesign capable of being rolled or folded into a small cross section thatcan fit through a relatively smaller incision. For example, the IOLs canbe of what is known as a one piece or multipiece design, and compriseoptic and haptic components. The optic is that portion which serves asthe lens. The haptics are attached to the optic and hold the optic inits proper place in the eye. The optic and haptic(s) can be of the sameor different material. A multipiece lens is so called because the opticand the haptic(s) are made separately and then the haptics are attachedto the optic. In a single piece lens, the optic and the haptics areformed out of one piece of material. Depending on the material, thehaptics are then cut, or lathed, out of the material to produce the IOL.

The invention will be further illustrated by the following examples,which are intended to be illustrative, but not limiting.

EXAMPLE 1 Synthesis of 4-phenylbutyl methacrylate (“PBMA”)

A three neck round bottom flask containing a teflon coated magneticstirring bar was successively charged with 120 mL (1.09 mol) of methylmethacrylate (2), 5.35 g (0.015 mol) of titanium tetrabutoxide(Ti(OC₄H₉)₄), 60 mL (0.39 mol) of 4-phenyl-1-butanol (1), and 14.6 g(0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel,thermometer, and a short path still head with thermometer and receiverflask were placed in the flask necks. The flask was placed in an oilbath and the temperature was increased until distillation began. Methylmethacrylate (2) was placed in the addition funnel and was addeddropwise at the same rate as the distillate. The reaction mixture washeated for 4 hours and then cooled to room temperature. The crudeproduct was vacuum distilled to isolate 62.8 g (0.29 mol, 74%) of4-phenylbutyl methacrylate (3) as a clear, colorless liquid.

EXAMPLE 2 Synthesis of 3-benzyloxypropyl methacrylate

A three neck round bottom flask containing a teflon coated magneticstirring bar was successively charged with 95 mL (0.884 mol) of methylmethacrylate (2), 4.22 g (0.012 mol) of titanium tetrabutoxide(Ti(OC₄H₉)₄), 50 mL (0.316 mol) of 3-benzyloxy-1-propanol (1), and 14.6g (0.073 mol) of 4-benzyloxyphenol (4-BOP). An addition funnel,thermometer, and a short path still head with thermometer and receiverflask were placed in the flask necks. The flask was placed in an oilbath and the temperature was increased until distillation began. Methylmethacrylate (2) was placed in the addition funnel and was addeddropwise at the same rate as the distillate. The reaction mixture washeated for 4 hours and then cooled to room temperature. The crudeproduct was vacuum distilled to isolate 36.5 g (0.156 mol, 49%) of3-benzyloxypropyl methacrylate (3) as a clear, colorless liquid.

EXAMPLE 3 Preferred Intraocular Lens Material

A preferred intraocular lens material is presented below. All amountsare expressed as % by weight. This formulation can be initiated with aperoxy free-radical initiator, such as 1%di-(4-t-butylcyclohexyl)peroxydicarbonate (“PERK16S”)

Ingredient % (w/w) PBMA 82-84 PDMS (MW = 800-1400) 0.5-2   PEG(1000)DMA13-15 EGDMA 1 UV absorber 0.1-5   Blue-light absorber 0.01-0.5 

The chemicals are weighed, mixed, and filtered together. The resultingformulation solution is flushed with nitrogen gas and then transferredto a glovebox with a low oxygen atmosphere. The formulation is pipettedinto degassed polypropylene molds. The assembled molds are thentransferred to an oven and cured at 90° C. for 1 hour, followed by apost-cure at 110° C. for 1 hour. The polymer samples are removed fromthe molds after cooling. The low tack property of the samples isnoticeable at this step of the preparation. The samples are extractedwith acetone and vacuum dried. Subsequent tack evaluations show thematerials are less tacky than control samples not containing PDMS.

EXAMPLES 4-10

Each of the formulations of Examples 4-10 was prepared as follows. Ineach case, the “PDMS” was dimethylacryloxypropyl-terminatedpolydimethylsiloxane (R₁═R₂═R₃═CH₃, and z=3).

Monomers were weighed into amber glass scintillation vials withteflon-lined screw-caps. The vials are shaken 1 hr on an orbital shakeruntil the liquid PDMS formed a uniform, clear solution. Then theinitiator was added to the sample in an amount equal to about 1% of thetotal formulation weight. The initiator for each sample was PERK16S.After filtering the sample through a 1-micron glass fiber membranesyringe filter connected to a 5-mL latex-free, oil-free syringe, theformulation was purged with nitrogen for 5-15 min and then capped tokeep out air. Samples were cast into polypropylene slab or lens molds ina glovebox (a containment device which provides a microenvironment of adry nitrogen atmosphere with less than 50-140 ppm oxygen). To maintainthe mold geometry during curing, spring clamps are used on the slabmolds. The slab and lens molds were previously prepared by heating at90° C. for more than 2 hrs. under vacuum (less than 0.1 in Hg pressure),then transferring the molds to the glovebox. After filling the molds,the samples were transferred from the glove box to a curing oven andheated for 1 hr. at 90° C., followed by 1 hr. at 110° C. The sampleswere cooled to room temperature and then stored briefly in the freezerbefore opening the molds. After opening the molds, the cured sampleswere extracted in acetone to remove any materials not bound to thecross-linked network and then dried in air. Finally, the samples wereplaced into polypropylene tissue capsules and then into a vacuum ovenand dried under vacuum at 60-63° C. and below 0.1 inches Hg pressure.The samples were inspected visually to record whether they were clear.

Physical property data labeled “Stress at Break, “Strain at Break”,“Young's Modulus,” “25% Secant Modulus,” and “100% Secant Modulus” inthe tables below was assessed according to the methods referred toabove. “Quantitative Tack” was determined by the following method. Thetack testing apparatus has two parts: a bottom component attached to thelower stationary Instron grip and a top component attached to the uppermovable Instron grip. At the center of the bottom component is a 4-mmdiameter cylindrical stainless steel stage attached on its end and thusstanding vertical. Testing specimens are placed on the exposed end ofthe stage which is finely polished to mimic the finish on most stainlesssteel surgical instruments. The top component contains a 4.1-mm diametercircular opening that slides over the cylindrical stage as the topcomponent is lowered. During testing, the upper component is raised andthe edges of the circular opening contact the specimen and detach itfrom the cylindrical stage. In preparation for testing, the tack testingapparatus is mechanically fixed to an Instron testing instrument. Testspecimens are prepared by punching 6-mm disks out of polymer slabs witha die. Prior to each experimental run, the upper component of theapparatus is lowered so it is just below the top of the 5-mm diameterpolished stainless steel cylindrical stage at the center of the base. Itis important to verify that no part of the upper component in any waycontacts the cylinder. If any contact occurs, it will register a loadduring testing due to frictional forces and negatively impact thequality of the results. Once the top is set in place, a polymer disk isplaced on the stage, and a 50-g weight is then placed on the disk. Aftera one-minute equilibration time, the run is started. The testing methodsimply consists of raising the upper component of the apparatus at aconstant rate of 10 mm/min until the disk is fully separated from thecylinder. To maintain a clean and consistent contact surface, the lowerstage is cleaned with acetone and allowed to fully dry between samples.A load-displacement curve is generated for each run. This curve is usedfor calculating the energy (“Tack: Total Energy”) required to detach thesample from the cylinder. Detachment energy is determined by calculatingthe area under the load-displacement curve. Qualitative observationswere obtained by handling the samples with metal forceps (“Tackiness byHandling”).

Unless indicated otherwise, all ingredient amounts shown below arelisted as % (w/w). The following abbreviations are used in Tables 1-4:

-   -   PBMA: 4-phenylbutylmethacrylate    -   PDMS: dimethacryloxypropyl-terminated polydimethylsiloxane    -   PEG(1000)DMA: polyethylene glycol 1000 dimethacrylate    -   EGDMA: ethylene glycoldimethacrylate    -   BHMA:        2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenylethyl]methacrylate.

TABLE 1 INGREDIENT CONTROL EX. 4 PBMA 83.99 83.98 PDMS (MW = 800-1400) — 2.01 PEG(1000) DMA 15.00 12.99 EGDMA  1.01  1.02 Tack: Total Energy(mJ) 2.01 ± 0.24 0.62 ± 0.23 Tackiness by Handling Tacky Slightly tackyAppearance (dry) Clear Clear Appearance (in water @ 35° C.) N/A Clear

TABLE 2 INGREDIENT CONTROL EX. 5 EX. 6 EX. 7 PBMA 82.99 80.99  81.98 82.50  PDMS (MW = 800-1400) — 2.01 1.02 0.50 PEG (1000) DMA 15.01 15.00 15.00  14.99  EGDMA  0.99 1.00 1.00 1.00 BHMA  1.00 1.01 1.01 1.01 Tack:Total Energy (mJ) 1.47 ± 0.34 0.31 ± 0.06 0.55 ± 0.16 1.12 ± 0.35Appearance (dry) Clear Clear Clear Clear Stress @ break (mPa) 4.97 ±0.48 5.29 ± 0.46 5.69 ± 0.78 5.11 ± 0.43 Strain @ break (%) 102.4 ± 4.7 102.1 ± 5.8  107.0 ± 8.3  102.0 ± 4.5  Young's Modulus (MPa) 15.41 ±0.84  12.88 ± 0.88  13.60 ± 0.63  13.87 ± 0.68  25% Secant Modulus (mPa)5.97 ± 0.25 5.65 ± 0.19 5.77 ± 0.13 5.78 ± 0.13 100% Secant Modulus(mPa) 4.84 ± 0.26 5.06 ± 0.16 5.07 ± 0.28 4.96 ± 0.13

TABLE 3 INGREDIENT EX. 8 EX. 9 EX. 10 PBMA 83.98 79.87 77.95 PDMS (M_(n)550-700) 2.01 4.09 5.94 PEG (1000) DMA 12.99 15.04 15.06 EGDMA 1.02 1.001.05 Appearance Clear Clear Clear (uncured liquid formulation)Appearance (dry) Clear Clear Clear Tackiness by handling Slightly tackyTacky Tacky Conclusion Suitable for Unsuitable for Unsuitable foroptical uses optical uses optical uses

EXAMPLES 11 AND 12 Monosubstituted polydimethylsiloxane(methylacryloxypropyl-terminated polydimethylsiloxane) (“MonosubstitutedPDMS”)

The formulations shown below in Table 4 were prepared using theprocedure described in Examples 4-7 above. Unlike thedimethylacryloxypropyl-terminated polydimethylsiloxane of the presentinvention, mono-substituted polydimethylsiloxane did not produce clear,reduced tack materials suitable for use as IOL materials.

TABLE 4 INGREDIENT EX. 11 EX. 12 PBMA 83.97  83.87  Monosubstituted PDMS— 2.13 (M_(n) 800-1200) Monosubsituted PDMS 2.02 — (M_(n) 4K-6K) PEG(1000) DMA 12.99  12.98  EGDMA 1.02 1.02 Appearance Cloudy Clear(uncured liquid formulation) (micellar mixture) Appearance (dry) Notcured Hazy after curing Tackiness by handling Not applicable Slightlytacky Conclusion Unsuitable for Unsuitable for optical uses optical uses

1. A polymeric ophthalmic or otorhinolaryngological device materialcomprising a) a principal device-forming monomer which is an arylacrylic hydrophobic monomer of the formula

wherein: A is H, CH₃, CH₂CH₃, or CH₂OH; B is (CH₂)m or [O (CH₂)₂]_(n); Cis (CH₂)_(w); m is 2-6; n is 1-10; Y is nothing, O, S, or NR, providedthat if Y is O, S, or NR, then B is (CH₂)_(m); R is H, CH₃,C_(n)H_(2n+1)(n=1-10), iso-OC₃H₇, C₆H₅, or CH₂C₆H₅; w is 0-6, providedthat m+w≦8; and D is H, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₆H₅, CH₂C₆H₅ orhalogen, b) a dimethylacryloxypropyl-terminated polydimethylsiloxanemacromer in an amount effective to reduce the tack of the polymericophthalmic or otorhinolaryngological device material, wherein thedimethylacryloxypropyl-terminated polydimethylsiloxane macromer has theformula

wherein R₁ and R₂ are independently —CH₃, —CH₂CH₃, —CH₂CH₂CH₂CH₃,CH₂CH₂CH₂CH₃, —C₆H₅, —CH₂C₆H₅, —CH₂CH₂C₆H₅, —CH₂CH₂CH₂C₆H₅, or—CH₂CH₂CH₂CH₂C₆H₅; R₃ is H, CH₃, or CH₂CH₃; z is 2-11; and x indicatesthe number of repeating units and is such that the macromer has amolecular weight of about 300 about 3500; and c) a cross-linkingmonomer, wherein the principal device-forming monomer is present in anamount of at least about 75% (w/w), wherein thedimethylacryloxypropyl-terminated polydimethylsiloxane macromer ispresent in an amount from 0.5-3.9% (w/w), wherein the cross-linkingmonomer is present in an amount of about 0.01-17% (w/w).
 2. Thepolymeric ophthalmic or otorhinolaryngological device material of claim1 wherein A is CH₃, B is (CH₂)_(m), m is 2-5, Y is nothing or O, w is0-1, and D is H.
 3. The polymeric ophthalmic or otorhinolaryngologicaldevice material of claim 2 wherein the aryl acrylic hydrophobic monomeris selected from the group consisting of 4-phenylbutyl methacrylate;5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and3-benzyloxypropyl methacrylate.
 4. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 further comprising oneor more components selected from the group consisting of reactive UVabsorbers and reactive blue-light absorbers.
 5. The polymeric ophthalmicor otorhinolaryngological device material of claim 1 wherein thedimethylacryloxypropyl-terminated polydimethylsiloxane macromer ispresent in an amount from 0.5-2% (w/w).
 6. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 wherein thedimethylacryloxypropyl-terminated polydimethylsiloxane macromer ispresent in an amount from 0.8-1.2% (w/w).
 7. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 wherein R₁═R₂═CH₃; R₃is H, CH₃, or CH₂CH₃; z=3; and x=0-22.
 8. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 wherein x =5-14. 9.The polymeric ophthalmic or otorhinolaryngological device material ofclaim 1 wherein x=2-5.
 10. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 wherein the materialis an ophthalmic device material and has a refractive index of at least1.50.
 11. The polymeric ophthalmic or otorhinolaryngological devicematerial of claim 1 wherein the material has a Tg less than about +15°C.
 12. The polymeric ophthalmic or otorhinolaryngological devicematerial of claim 1 wherein the material has an elongation of at least90%.
 13. The polymeric ophthalmic or otorhinolaryngological devicematerial of claim 1 wherein the cross-linking component comprises one ormore cross-linking agents selected from the group consisting of ethyleneglycol dimethacrylate; diethylene glycol dimethacrylate; allylmethacrylate; 1,3-propanediol dimethacrylate; 2,3-propanedioldimethacrylate; 1,6-hexanediol dimethacrylate; 1,4-butanedioldimethacrylate; CH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂ wherep=1-50; CH₂═C(CH₃)C(═O)O(CH₂)_(t)OC(═O)C(CH₃)═CH₂ where t=3-20; andtheir corresponding acrylates.
 14. The polymeric ophthalmic orotorhinolaryngological device material of claim 1 wherein the principaldevice-forming monomer is present in an amount of at least about 80%(w/w).
 15. The polymeric ophthalmic or otorhinolaryngological devicematerial of claim 1 wherein the aryl acrylic hydrophobic monomer isselected from the group consisting of 4-phenylbutyl methacrylate;5-phenylpentyl methacrylate; 2-benzyloxyethyl methacrylate; and3-benzyloxypropyl methacrylate; and the cross-linking monomer isCH₂═C(CH₃)C(═O)O—(CH₂CH₂O)_(p)—C(═O)C(CH₃)═CH₂, where p is such that thenumber average molecular weight of the cross-linking monomer is about1000.
 16. An intraocular lens optic comprising the polymeric devicematerial of claim 1
 17. A device comprising the device material of claim1 wherein the device is selected from the group consisting of a contactlens; a keratoprosthesis, a corneal inlay or ring; an otologicalventilation tube; and a nasal implant.